JP6531936B2 - Positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of manufacturing positive electrode active material for non-aqueous electrolyte secondary battery - Google Patents

Positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of manufacturing positive electrode active material for non-aqueous electrolyte secondary battery Download PDF

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JP6531936B2
JP6531936B2 JP2015004438A JP2015004438A JP6531936B2 JP 6531936 B2 JP6531936 B2 JP 6531936B2 JP 2015004438 A JP2015004438 A JP 2015004438A JP 2015004438 A JP2015004438 A JP 2015004438A JP 6531936 B2 JP6531936 B2 JP 6531936B2
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浩史 川田
浩史 川田
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    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M10/00—Secondary cells; Manufacture thereof
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Description

本開示は、非水電解質二次電池用正極活物質、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法に関する。   The present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, and a method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery.

Ｌｉ層以外の遷移金属層にもＬｉが含有されたリチウム過剰型の複合酸化物は、充放電に関与するＬｉが多いことから、高容量正極材料として注目されている。例えば、特許文献１は、Ｏ２構造を有するリチウム過剰型の複合酸化物（以下、「Ｏ２リチウム過剰酸化物」という）を開示している。特許文献１では、当該Ｏ２リチウム過剰酸化物をリチウム二次電池の正極活物質に適用することで、電池の放電容量が向上すると記載されている。なお、Ｏ３構造を有するリチウム過剰型の複合酸化物（以下、「Ｏ３リチウム過剰酸化物」という）も知られている。   Lithium-excess type composite oxides in which Li is also contained in transition metal layers other than Li layers are attracting attention as high-capacity positive electrode materials because they are rich in Li involved in charge and discharge. For example, Patent Document 1 discloses a lithium excess type composite oxide having an O 2 structure (hereinafter referred to as “O 2 lithium excess oxide”). Patent Document 1 describes that the discharge capacity of the battery is improved by applying the O 2 lithium excess oxide to a positive electrode active material of a lithium secondary battery. A lithium excess type composite oxide having an O 3 structure (hereinafter referred to as “O 3 lithium excess oxide”) is also known.

特開２０１２−２０４２８１号公報JP 2012-204281 A

しかし、従来技術では、例えば、Ｌｉの移動が阻害され、正極活物質の容量が十分ではなかった。
本開示の一態様は、電池容量を向上させる非水電解質二次電池用正極活物質を提供する。 However, in the prior art, for example, the migration of Li was inhibited, and the capacity of the positive electrode active material was not sufficient.
One aspect of the present disclosure provides a positive electrode active material for a non-aqueous electrolyte secondary battery that improves battery capacity.

本開示の一態様に係る非水電解質二次電池用正極活物質は、Ｘ線回折パターンの回折角１８°〜１９°にそれぞれピークトップがある２つのピークを持ち、当該各ピークのうち、低角度側ピークの強度Ａに対する高角度側ピークの強度Ｂの比Ｒ(B/A)が０．００１＜Ｒ(B/A)＜０．０３を満たすＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体｛Ｍは少なくとも１種の金属元素｝を含む。 The positive electrode active material for a non-aqueous electrolyte secondary battery according to an aspect of the present disclosure has two peaks each having a peak top at a diffraction angle of 18 ° to 19 ° in an X-ray diffraction pattern, and among the respective peaks, low. Li 2 MnO 3 -LiMO 2 solid solution {M is a ratio R (B / A) of the intensity B of the high angle side peak to the intensity A of the angle side peak satisfying 0.001 <R (B / A) <0.03 Containing at least one metal element}.

本開示に係る非水電解質二次電池用正極活物質によれば、従来のリチウム過剰酸化物を用いた正極活物質よりも、電池容量を向上させることができる。   According to the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present disclosure, the battery capacity can be improved as compared with a conventional positive electrode active material using a lithium excess oxide.

本開示の実施形態の一例である正極活物質のＸ線回折パターンである。It is a X-ray-diffraction pattern of the positive electrode active material which is an example of embodiment of this indication. 本開示の実施形態の一例である正極活物質の作製に用いられるナトリウム複合酸化物のＸ線回折パターンである。It is a X-ray-diffraction pattern of sodium complex oxide used for preparation of the positive electrode active material which is an example of embodiment of this indication. 実施例及び比較例で作製した非水電解質二次電池を模式的に示す図である。It is a figure which shows typically the nonaqueous electrolyte secondary battery produced by the Example and the comparative example. 実施例及び比較例で作製した非水電解質二次電池において、正極活物質のＸ線回折パターンにおけるピーク強度比Ｒ(B/A)と、放電容量との関係を示す図である。In the nonaqueous electrolyte secondary battery manufactured by the Example and the comparative example, it is a figure which shows the relationship between peak intensity ratio R (B / A) in the X-ray-diffraction pattern of a positive electrode active material, and discharge capacity. 実施例及び比較例で作製した非水電解質二次電池において、正極活物質の作製に用いられるナトリウム複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)と、放電容量との関係を示す図である。In the non-aqueous electrolyte secondary batteries produced in Examples and Comparative Examples, the relationship between the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the sodium composite oxide used for producing the positive electrode active material and the discharge capacity FIG.

（本開示の基礎となった知見）
従来技術においては、Ｏ３リチウム過剰酸化物を正極活物質に用いた場合は、充放電中に遷移金属がマイグレーションして、アルカリ金属層中におけるＬｉの移動が阻害されるという課題がある。一方、Ｏ２リチウム過剰酸化物を正極活物質に用いた場合は、上記マイグレーションの問題は解消されるが、Ｏ３構造と比べて遷移金属層からアルカリ金属層へのパスが狭く、遷移金属層中でＬｉが移動し難いという課題がある。このため、従来のリチウム過剰酸化物を用いた正極活物質では、期待されるほどの容量が得られていない。
これらの課題に対して、本発明者は、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体を含む（例えば、主成分として含む）、リチウム過剰型の正極活物質において、Ｘ線回折パターンの２つの所定ピークの強度比が特定の範囲内である場合に、電池容量が特異的に向上することを見出した。
本開示の一態様に係る非水電解質二次電池用正極活物質は、Ｘ線回折パターンの回折角１８°〜１９°にそれぞれピークトップがある２つのピークを持ち、当該各ピークのうち、低角度側ピークの強度Ａに対する高角度側ピークの強度Ｂの比Ｒ(B/A)が０．００１＜Ｒ(B/A)＜０．０３を満たすＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体｛Ｍは少なくとも１種の金属元素｝を含む。
これにより、従来のリチウム過剰酸化物を用いた正極活物質よりも、電池容量を向上させることができる。 (Findings that formed the basis of this disclosure)
In the prior art, when an O3 lithium excess oxide is used as a positive electrode active material, there is a problem that the transition metal migrates during charge and discharge, thereby inhibiting the movement of Li in the alkali metal layer. On the other hand, when the O2 lithium excess oxide is used as the positive electrode active material, the above-mentioned migration problem is solved, but the path from the transition metal layer to the alkali metal layer is narrower than in the O3 structure, and the transition metal layer There is a problem that Li is difficult to move. For this reason, in the positive electrode active material using the conventional lithium excess oxide, an expected capacity is not obtained.
With respect to these problems, the present inventors have found that in the lithium-excess type positive electrode active material containing (for example, as a main component) a Li 2 MnO 3 -LiMO 2 solid solution, two predetermined peaks of the X-ray diffraction pattern It has been found that the battery capacity is specifically improved when the intensity ratio is within the specific range.
The positive electrode active material for a non-aqueous electrolyte secondary battery according to an aspect of the present disclosure has two peaks each having a peak top at a diffraction angle of 18 ° to 19 ° in an X-ray diffraction pattern, and among the respective peaks, low. Li 2 MnO 3 -LiMO 2 solid solution {M is a ratio R (B / A) of the intensity B of the high angle side peak to the intensity A of the angle side peak satisfying 0.001 <R (B / A) <0.03 Containing at least one metal element}.
Thereby, the battery capacity can be improved as compared with the conventional positive electrode active material using an excess lithium oxide.

以下、本開示の実施形態の一例について詳説する。
本開示の実施形態の一例である非水電解質二次電池は、正極と、負極と、非水電解質とを備える。正極と負極との間には、セパレータを設けることが好適である。非水電解質二次電池は、例えば、正極及び負極がセパレータを介して巻回されてなる巻回型の電極体と、非水電解質とが外装体に収容された構造を有する。或いは、巻回型の電極体の代わりに、正極及び負極がセパレータを介して積層されてなる積層型の電極体など、他の形態の電極体が適用されてもよい。また、非水電解質二次電池の形態としては、特に限定されず、円筒型、角型、コイン型、ボタン型、ラミネート型などが例示できる。 Hereinafter, an example of an embodiment of the present disclosure will be described in detail.
A non-aqueous electrolyte secondary battery, which is an example of an embodiment of the present disclosure, includes a positive electrode, a negative electrode, and a non-aqueous electrolyte. It is preferable to provide a separator between the positive electrode and the negative electrode. The non-aqueous electrolyte secondary battery has, for example, a structure in which a non-aqueous electrolyte and a wound-type electrode body in which a positive electrode and a negative electrode are wound via a separator are accommodated in an outer package. Alternatively, instead of the wound type electrode body, another form of electrode body may be applied, such as a stacked type electrode body in which a positive electrode and a negative electrode are stacked via a separator. The form of the non-aqueous electrolyte secondary battery is not particularly limited, and may be cylindrical, square, coin, button or laminate.

〔正極〕
正極は、例えば金属箔等の正極集電体と、正極集電体上に形成された正極活物質層とで構成される。正極集電体には、アルミニウムなどの正極の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。正極活物質層は、正極活物質の他に、導電材及び結着材を含むことが好適である。 [Positive electrode]
The positive electrode is composed of, for example, a positive electrode current collector such as a metal foil and a positive electrode active material layer formed on the positive electrode current collector. As the positive electrode current collector, a foil of a metal stable in the potential range of the positive electrode such as aluminum, a film in which the metal is disposed on the surface, or the like can be used. The positive electrode active material layer preferably contains a conductive material and a binder in addition to the positive electrode active material.

導電材は、正極活物質層の電気伝導性を高めるために用いられる。導電材としては、カーボンブラック、アセチレンブラック、ケッチェンブラック、黒鉛等の炭素材料が例示できる。これらは、単独で用いてもよく、２種類以上を組み合わせて用いてもよい。導電材の含有率は、正極活物質層の総質量に対して０．１〜３０重量％が好ましく、０．１〜２０重量％がより好ましく、０．１〜１０重量％が特に好ましい。   The conductive material is used to enhance the electrical conductivity of the positive electrode active material layer. Examples of the conductive material include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more. 0.1-30 weight% is preferable with respect to the gross mass of a positive electrode active material layer, 0.1-20 weight% is more preferable, and, as for the content rate of a electrically conductive material, 0.1-10 weight% is especially preferable.

結着材は、正極活物質及び導電材間の良好な接触状態を維持し、且つ正極集電体表面に対する正極活物質等の結着性を高めるために用いられる。結着剤には、例えばポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン、ポリビニルアセテート、ポリメタクリレート、ポリアクリレート、ポリアクリロニトリル、ポリビニルアルコール、又はこれらの２種以上の混合物等が用いられる。結着材は、カルボキシメチルセルロース（ＣＭＣ）、ポリエチレンオキシド（ＰＥＯ）等の増粘剤と併用されてもよい。これらは、単独で用いてもよく、２種類以上を組み合わせて用いてもよい。結着剤の含有率は、正極活物質層の総質量に対して０．１〜３０重量％が好ましく、０．１〜２０重量％がより好ましく、０．１〜１０重量％が特に好ましい。   The binder is used to maintain good contact between the positive electrode active material and the conductive material, and to enhance the binding of the positive electrode active material or the like to the surface of the positive electrode current collector. As the binder, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl acetate, polymethacrylate, polyacrylate, polyacrylonitrile, polyvinyl alcohol, or a mixture of two or more of these, and the like are used. The binder may be used in combination with a thickener such as carboxymethylcellulose (CMC) or polyethylene oxide (PEO). These may be used alone or in combination of two or more. The content of the binder is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, and particularly preferably 0.1 to 10% by weight, based on the total weight of the positive electrode active material layer.

正極の充電終止電位（満充電状態での正極電位）は、特に限定されないが、好ましくは４．４Ｖ（ｖｓ．Ｌｉ／Ｌｉ+）以上であり、より好ましくは４．５Ｖ以上であり、特に好ましくは４．５Ｖ〜５．０Ｖである。本非水電解質二次電池は、充電終止電圧が４．４Ｖ以上の高電圧用途において特に好適である。 The charge termination potential of the positive electrode (positive electrode potential in a fully charged state) is not particularly limited, but is preferably 4.4 V (vs. Li / Li + ) or more, more preferably 4.5 V or more, particularly preferably Is 4.5V to 5.0V. The non-aqueous electrolyte secondary battery is particularly suitable for high voltage applications in which the charge termination voltage is 4.4 V or more.

以下、正極活物質について詳説する。
正極活物質は、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体｛Ｍは少なくとも１種の金属元素｝を含む。例えば、主成分として含んでもよい。ここで、主成分とは、正極活物質の総体積に対して５０体積％以上含まれていることを示す。Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、Ｌｉ層以外の遷移金属層にもＬｉが含有されたリチウム過剰型のリチウム複合酸化物である。Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体のＸ線回折測定により得られるＸ線回折パターンには、回折角（２θ）２０°〜２５°付近に超格子構造に由来するピークが観測される（図１のＸ線回折パターンでは、２θ＝２１°付近に現れている）。 Hereinafter, the positive electrode active material will be described in detail.
The positive electrode active material contains Li 2 MnO 3 -LiMO 2 solid solution {M is at least one metal element}. For example, it may be contained as a main component. Here, the term "main component" means that the content is 50% by volume or more based on the total volume of the positive electrode active material. The Li 2 MnO 3 -LiMO 2 solid solution is a lithium-rich lithium complex oxide in which Li is also contained in transition metal layers other than the Li layer. In the X-ray diffraction pattern obtained by X-ray diffraction measurement of the Li 2 MnO 3 -LiMO 2 solid solution, a peak derived from the superlattice structure is observed around the diffraction angle (2θ) of 20 ° to 25 ° (FIG. In the X-ray diffraction pattern, it appears around 2θ = 21 °).

なお、正極活物質は、本開示の目的を損なわない範囲で、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体と異なる他の金属化合物等を混合物や固溶体の形で含んでいてもよい。但し、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、正極活物質の総体積に対して５０体積％以上含まれていることが好ましく、８０体積％以上がより好ましい。本実施形態では、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体のみ（１００体積％）から正極活物質が構成されているものとする。 Note that the positive electrode active material may contain, in the form of a mixture or a solid solution, another metal compound or the like different from the Li 2 MnO 3 -LiMO 2 solid solution, as long as the object of the present disclosure is not impaired. However, Li 2 MnO 3 -LiMO 2 solid solution is preferably contained more than 50% by volume relative to the total volume of the positive electrode active material, more preferably at least 80% by volume. In the present embodiment, it is assumed that the positive electrode active material is composed of only Li 2 MnO 3 -LiMO 2 solid solution (100% by volume).

Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体（正極活物質）のＭは、例えばＮｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｍｇ、Ｔｉ、Ｓｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｗ、Ｂｉ、Ｃｒ、Ｖ、Ｃｅ、Ｋ、Ｇａ、及びＩｎから選択される少なくとも１種である。Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、遷移金属として、Ｍｎの他にＮｉ及びＣｏの少なくとも一方を含有することが好ましく、Ｎｉ及びＣｏの両方を含有することがより好ましい。 M of Li 2 MnO 3 -LiMO 2 solid solution (positive electrode active material) is, for example, Ni, Co, Fe, Al, Mg, Ti, Sn, Zr, Nb, Mo, W, Bi, Cr, V, Ce, K, It is at least one selected from Ga and In. The Li 2 MnO 3 -LiMO 2 solid solution preferably contains at least one of Ni and Co in addition to Mn as a transition metal, and more preferably contains both Ni and Co.

例えば、一般式ＬｉxＮａy[Ｌｉz1Ｍｎz2Ｍ* (1-z1-z2)]Ｏ(2±z)｛０．６７＜ｘ＜１．１、０＜ｙ＜０．１、０＜ｚ１＜０．３３、０．５＜ｚ２＜０．９５、０≦γ＜０．１、Ｍ*は少なくともＮｉ、Ｃｏを含む、２種以上の金属元素｝で表されるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体が好適である。 For example, the general formula Li x Na y [Li z1 Mn z2 M * (1-z1-z2)] O (2 ± z) {0.67 <x <1.1,0 <y <0.1,0 < Li 2 MnO 3 − represented by z1 <0.33, 0.5 <z2 <0.95, 0 ≦ γ <0.1, M * at least Ni and two or more metal elements including Co} LiMO 2 solid solution is preferred.

上記一般式において、ｘを０．６７よりも大きくすることで高容量化を図ることができる。但し、正極活物質表面における残留アルカリ量の抑制等の観点から、ｘは１．１未満が好ましい。より好ましくは、０．８３＜ｘ＜１．１である。ｚ１は０よりも大きく、これは遷移金属層にＬｉが含まれることを意味する。高電位における結晶構造の安定性を考慮すると、ｚ１は０．３３未満が好ましい。   In the above general formula, the capacity can be increased by setting x larger than 0.67. However, x is preferably less than 1.1 from the viewpoint of suppressing the amount of residual alkali on the surface of the positive electrode active material, and the like. More preferably, 0.83 <x <1.1. z1 is greater than 0, which means that the transition metal layer contains Li. In view of the stability of the crystal structure at high potentials, z1 is preferably less than 0.33.

Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、上記一般式に示すように、少量のＮａを含有することが好適である。具体的には、上記一般式におけるｙは０．０００１以上０．１未満が好ましい。これにより、例えば高い容量を維持しながら、Ｌｉが移動する面間隔を広げて充放電特性を向上させることができる。 The Li 2 MnO 3 -LiMO 2 solid solution preferably contains a small amount of Na as shown in the above general formula. Specifically, y in the above general formula is preferably 0.0001 or more and less than 0.1. As a result, for example, while maintaining a high capacity, it is possible to widen the surface distance in which Li moves, and to improve the charge and discharge characteristics.

図１は、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体（正極活物質）のＸ線回折パターンである。
図１に示すように、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体のＸ線回折測定により得られるＸ線回折パターンには、２θ＝１８°〜１９°にそれぞれピークトップがある２つのピークが存在する。即ち、正極活物質は、Ｘ線回折パターンの２θ＝１８°〜１９°にそれぞれピークトップがある２つのピークを持つＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体を主成分（本実施形態では１００体積％）とする。 FIG. 1 is an X-ray diffraction pattern of Li 2 MnO 3 -LiMO 2 solid solution (positive electrode active material).
As shown in FIG. 1, in the X-ray diffraction pattern obtained by X-ray diffraction measurement of the Li 2 MnO 3 -LiMO 2 solid solution, two peaks each having a peak top at 2θ = 18 ° to 19 ° exist. That is, the positive electrode active material is mainly composed of Li 2 MnO 3 -LiMO 2 solid solution having two peaks with peak tops at 2θ = 18 ° to 19 ° in the X-ray diffraction pattern (100% by volume in this embodiment) I assume.

さらに、正極活物質の主成分であるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、当該各ピークのうち、低角度側ピークの強度Ａに対する高角度側ピークの強度Ｂの比Ｒ(B/A)が、０．００１＜Ｒ(B/A)＜０．０３を満たすものである。ピーク強度比Ｒ(B/A)が当該範囲内にあるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体を用いた正極活物質は、後述の実施例に示すように、放電容量を特異的に向上させる。 Furthermore, in the Li 2 MnO 3 -LiMO 2 solid solution that is the main component of the positive electrode active material, the ratio R (B / A) of the intensity B of the high angle side peak to the intensity A of the low angle side peak is , 0.001 <R (B / A) <0.03. The positive electrode active material using a Li 2 MnO 3 -LiMO 2 solid solution in which the peak intensity ratio R (B / A) is in the above range specifically improves the discharge capacity as shown in the examples described later.

Ｘ線回折パターンの２θ＝１８°〜１９°における２つのピークの存在は、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体が２つの異なる結晶構造を有していることを示す。低角度側ピークの強度Ａは高角度側ピークの強度Ｂに比べて大幅に大きく、このことはＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体の主たる結晶構造に由来するピークが低角度側ピークであることを意味する。即ち、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、主たる結晶構造に加えて、これと異なる結晶構造をわずかに有している。 The presence of two peaks at 2θ = 18 ° -19 ° of the X-ray diffraction pattern indicates that the Li 2 MnO 3 -LiMO 2 solid solution has two different crystal structures. The intensity A of the low angle side peak is significantly larger than the intensity B of the high angle side peak, which means that the peak derived from the main crystal structure of the Li 2 MnO 3 -LiMO 2 solid solution is the low angle side peak means. That is, in addition to the main crystal structure, the Li 2 MnO 3 -LiMO 2 solid solution slightly has a crystal structure different from this.

低角度側ピークは、Ｏ２構造、Ｔ２構造、Ｏ６構造、又はこれらの混合に起因するものである。即ち、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体の主たる結晶構造は、Ｏ２構造、Ｔ２構造、Ｏ６構造、又はこれらが混合した構造である。Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体の主たる結晶構造は、例えばＯ２構造である。なお、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、Ｏ２構造のみから構成されていてもよいが、Ｏ２構造の当該固溶体を合成する際に副生成物としてＴ２構造、Ｏ６構造の酸化物が合成される場合がある。 The low angle side peak is due to the O2 structure, the T2 structure, the O6 structure, or a mixture thereof. That is, the main crystal structure of the Li 2 MnO 3 -LiMO 2 solid solution is the O 2 structure, the T 2 structure, the O 6 structure, or a structure in which these are mixed. Main crystal structure of Li 2 MnO 3 -LiMO 2 solid solution is, for example, O2 structure. Incidentally, Li 2 MnO 3 -LiMO 2 solid solution may be composed of only O2 structure but, T2 structure as a by-product, oxides of O6 structure is synthesized in the synthesis of the solid solution of the O2 structure There is a case.

ここで、Ｏ２構造とは、空間群Ｐ６３ｍｃに属し、Ｌｉが酸素８面体の中心に存在し、且つ酸素と遷移金属との重なり方が単位格子あたり２種類存在する構造である。Ｏ６構造とは、空間群Ｒ−３ｍに属し、Ｌｉが酸素８面体の中心に存在し、且つ酸素と遷移金属との重なり方が単位格子あたり６種類存在する構造である。また、Ｔ２構造とは、空間群Ｃｍｃａに属し、Ｌｉが酸素４面体の中心に存在し、且つ酸素と遷移金属との重なり方が単位格子あたり２種類存在する構造である。   Here, the O2 structure is a structure belonging to the space group P63 mc, in which Li is present at the center of the oxygen octahedron, and two types of oxygen and transition metal overlap exist per unit cell. The O6 structure belongs to the space group R-3m, is a structure in which Li is present at the center of the oxygen octahedron and there are six types of oxygen and transition metal overlapping patterns per unit cell. The T2 structure is a structure belonging to the space group Cmca, in which Li is present at the center of the oxygen tetrahedron, and in which two types of oxygen and transition metal overlap exist per unit cell.

高角度側ピークは、酸素が立方最密充填された構造(以下、「ｃｃｐ構造」という)に起因するものである。具体的には、空間群Ｒ−３ｍ又はＣ２／ｍに属するＯ３構造、空間群Ｆｄ３ｍに属するスピネル構造、又はこれらの混合に起因する。即ち、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体にわずかに含まれる結晶構造は、ｃｃｐ構造であって、例えばＯ３構造である。なお、Ｏ３構造は、空間群Ｒ−３ｍに属し、Ｌｉが酸素８面体の中心に存在し、且つ酸素と遷移金属との重なり方が単位格子あたり３種類存在する構造である。 The high angle side peak is attributable to a structure in which oxygen is closely packed in cubic (hereinafter referred to as "ccp structure"). Specifically, it originates in the O3 structure which belongs to space group R-3m or C2 / m, the spinel structure which belongs to space group Fd3m, or these mixtures. That is, the crystal structure slightly contained in the Li 2 MnO 3 -LiMO 2 solid solution is a ccp structure, for example, an O 3 structure. The O3 structure belongs to the space group R-3m, is a structure in which Li is present at the center of the oxygen octahedron, and three types of oxygen and transition metal overlap exist per unit lattice.

上記Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、ナトリウム複合酸化物を合成した後、当該複合酸化物のＮａをＬｉにイオン交換することによって作製することができる。 The Li 2 MnO 3 -LiMO 2 solid solution, after synthesizing a sodium complex oxide, the Na of the composite oxide can be prepared by ion-exchange Li.

ナトリウム複合酸化物の合成方法は、以下の通りである。
ナトリウム複合酸化物は、ＬｉよりもＮａの含有量が多い複合酸化物であって、例えばナトリウム化合物、リチウム化合物、及び遷移金属化合物を混合し、当該混合物を焼成することにより合成することができる。ナトリウム化合物としては、例えばＮａ2Ｏ、Ｎａ2Ｏ2、Ｎａ2ＣＯ3、ＮａＮＯ3、ＮａＯＨ等が挙げられる。リチウム化合物としては、例えばＬｉ2Ｏ、Ｌｉ2ＣＯ3、ＬｉＮＯ3、ＬｉＮＯ2、ＬｉＯＨ、ＬｉＯＨ・Ｈ2Ｏ、ＬｉＨ、ＬｉＦ等が挙げられる。遷移金属化合物には、Ｍｎを含有するマンガン化合物、他の遷移金属を含有する化合物（例えば、ニッケル化合物、コバルト化合物）が用いられる。マンガン化合物としては、例えばＭｎ3Ｏ4、Ｍｎ2Ｏ3、ＭｎＯ2、ＭｎＣＯ3、ＭｎＳＯ4、Ｍ
ｎ（ＯＨ）2等が挙げられる。 The synthesis method of sodium complex oxide is as follows.
The sodium composite oxide is a composite oxide having a higher content of Na than Li, and can be synthesized, for example, by mixing a sodium compound, a lithium compound, and a transition metal compound, and calcining the mixture. Examples of the sodium compound include Na 2 O, Na 2 O 2 , Na 2 CO 3 , NaNO 3 , NaOH and the like. Examples of the lithium compound include Li 2 O, Li 2 CO 3 , LiNO 3 , LiNO 2 , LiOH, LiOH · H 2 O, LiH, LiF and the like. As a transition metal compound, a manganese compound containing Mn and a compound containing another transition metal (for example, a nickel compound or a cobalt compound) are used. As a manganese compound, for example, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , MnCO 3 , MnSO 4 , M
n (OH) 2 etc. are mentioned.

ナトリウム化合物、リチウム化合物、マンガン化合物、及び他の遷移金属化合物（ニッケル化合物、コバルト化合物）の混合比率は、ナトリウム複合酸化物のＸ線回折パターンにおける後述のピーク強度比Ｒ(b/a)が特定範囲となるように決定される。具体的には、Ｏ２リチウム過剰酸化物を作製する場合よりも、やや過剰のリチウム化合物を混合する。このとき、リチウム化合物の量が多すぎると、ピーク強度比Ｒ(b/a)が特定範囲を超えて目的とするナトリウム複合酸化物が得られないため、厳密な添加量調整が不可欠である。混合方法は、これらを均一に混合できるものであれば特に限定されず、ミキサー等の公知の混合機を用いた混合が例示できる。 The mixing ratio of sodium compounds, lithium compounds, manganese compounds, and other transition metal compounds (nickel compounds, cobalt compounds ) is determined by the peak intensity ratio R (b / a) described later in the X-ray diffraction pattern of the sodium composite oxide. It is decided to be a range. Specifically, a slight excess of lithium compound is mixed as compared to the case of producing an O 2 lithium excess oxide. At this time, if the amount of the lithium compound is too large, the peak intensity ratio R (b / a) exceeds a specific range, and the desired sodium composite oxide can not be obtained. The mixing method is not particularly limited as long as it can uniformly mix these, and can be exemplified mixing using a known mixer such as a mixer.

上記混合物の焼成は、大気中又は酸素気流中で行う。焼成温度は、６００〜１１００℃が好ましく、７００〜１０００℃がより好ましい。焼成時間は、焼成温度が６００〜１１００℃の場合、好ましくは１〜５０時間である。焼成物は、公知の方法で粉砕することが好ましい。   The firing of the above mixture is performed in the air or in an oxygen stream. 600-1100 degreeC is preferable and 700-1000 degreeC of a calcination temperature is more preferable. The firing time is preferably 1 to 50 hours when the firing temperature is 600 to 1100 ° C. The fired product is preferably ground by a known method.

図２は、上記の方法により得られるナトリウム複合酸化物のＸ線回折パターンである。
図２に示すように、ナトリウム複合酸化物のＸ線回折測定により得られるＸ線回折パターンには、２θ＝１６°〜１７°にピークトップがある第１ピークと、２θ＝１８°〜１９°にピークトップがある第２ピークとが存在する。即ち、正極活物質の主成分であるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、Ｘ線回折パターンの当該第１及び第２ピークを持つナトリウム複合酸化物から作製される。 FIG. 2 is an X-ray diffraction pattern of sodium complex oxide obtained by the above method.
As shown in FIG. 2, in the X-ray diffraction pattern obtained by X-ray diffraction measurement of the sodium composite oxide, a first peak having a peak top at 2θ = 16 ° to 17 ° and 2θ = 18 ° to 19 ° And a second peak with a peak top. That, Li 2 MnO 3 -LiMO 2 solid solution which is a main component of a positive electrode active material is prepared from the sodium complex oxide having the first and second peaks of the X-ray diffraction pattern.

さらに、上記ナトリウム複合酸化物は、第１ピークの強度ａに対する第２ピークの強度ｂの比Ｒ(b/a)が、０．００１＜Ｒ(b/a)＜０．０２８を満たすものである。第１ピーク及び第２ピークの存在は、ナトリウム複合酸化物が２つの異なる結晶構造を有していることを示す。当該ナトリウム複合酸化物のイオン交換により、上記Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体を作製することができる。 Furthermore, in the sodium complex oxide, the ratio R (b / a) of the intensity b of the second peak to the intensity a of the first peak satisfies 0.001 <R (b / a) <0.028. is there. The presence of the first peak and the second peak indicates that the sodium composite oxide has two different crystal structures. By the ion exchange of the sodium complex oxide, the above-mentioned Li 2 MnO 3 -LiMO 2 solid solution can be produced.

上記ナトリウム複合酸化物は、一般式Ｎａα[Ｌｉβ1Ｍｎβ2Ｍ(1-β1-β2)]Ｏ(2±z)｛０．６７＜α＜１．１、０＜β１＜０．３３、０．５＜β２＜０．９５、０≦γ＜０．１、Ｍは少なくとも１種の金属元素｝で表されるものが好適である。金属元素Ｍは、例えばＮｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｍｇ、Ｔｉ、Ｓｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｗ、Ｂｉ、Ｃｒ、Ｖ、Ｃｅ、Ｋ、Ｇａ、及びＩｎから選択される少なくとも１種である。ナトリウム複合酸化物は、遷移金属として、Ｍｎの他にＮｉ及びＣｏの少なくとも一方を含有することが好ましく、Ｎｉ及びＣｏの両方を含有することがより好ましい。 The sodium complex oxide is represented by the general formula Naα [Liβ 1 Mnβ 2 M ( 1- β 1- β 2)] O (2 ± z) {0.67 <α <1.1,0 <β1 <0.33 Those represented by 0.5 <β2 <0.95, 0 ≦ γ <0.1, M is at least one metal element} are preferable. The metal element M is, for example, at least one selected from Ni, Co, Fe, Al, Mg, Ti, Sn, Zr, Nb, Mo, W, Bi, Cr, V, Ce, K, Ga, and In. is there. The sodium composite oxide preferably contains, as a transition metal, at least one of Ni and Co in addition to Mn, and more preferably contains both Ni and Co.

イオン交換の方法は、以下の通りである。
ＮａをＬｉにイオン交換する好適な方法としては、例えばリチウム塩の溶融塩床をナトリウム複合酸化物に加えて加熱する方法が挙げられる。リチウム塩には、ＬｉＮＯ3、ＬｉＮＯ2、Ｌｉ2ＳＯ4、ＬｉＣｌ、Ｌｉ2ＣＯ3、ＬｉＯＨ、ＬｉＩ、ＬｉＢｒ等から選択される少なくとも１種を用いることが好ましい。イオン交換処理時における加熱温度は、１８０〜３８０℃が好ましく、２３０〜３３０℃がより好ましい。 The method of ion exchange is as follows.
As a suitable method of ion-exchange Na to Li, for example, a method of adding a molten salt bed of lithium salt to sodium complex oxide and heating it can be mentioned. The lithium salt is preferably at least one selected from LiNO 3 , LiNO 2 , Li 2 SO 4 , LiCl, Li 2 CO 3 , LiOH, LiI, LiBr and the like. 180-380 degreeC is preferable and, as for the heating temperature at the time of an ion exchange treatment, 230-330 degreeC is more preferable.

上記イオン交換処理の方法としては、少なくとも１種のリチウム塩を含む溶液中にナトリウム複合酸化物を浸漬する方法も適している。この場合は、リチウム化合物を溶解させた溶剤中にナトリウム複合酸化物を投入し、加熱処理する。イオン交換速度を高めるため、溶剤の沸点付近で溶媒を還流させながら、又は加圧することで沸騰を抑制した状態でイオン交換処理することが好ましい。処理温度は８０〜２００℃が好ましく、１００〜１８０℃がより好ましい。   As the method of the ion exchange treatment, a method of immersing sodium complex oxide in a solution containing at least one lithium salt is also suitable. In this case, the sodium composite oxide is placed in a solvent in which the lithium compound is dissolved, and heat treatment is performed. In order to increase the ion exchange rate, it is preferable to carry out the ion exchange treatment while refluxing the solvent in the vicinity of the boiling point of the solvent or in a state where boiling is suppressed by pressurizing. 80-200 degreeC is preferable and 100-180 degreeC of a process temperature is more preferable.

以上の工程により、Ｘ線回折パターンのピーク強度比Ｒ(B/A)が特定の範囲内（０．００１＜Ｒ(B/A)＜０．０３）にあるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体が得られる。 A Li 2 MnO 3 -LiMO 2 solid solution in which the peak intensity ratio R (B / A) of the X-ray diffraction pattern is within a specific range (0.001 <R (B / A) <0.03) by the above steps Is obtained.

〔負極〕
負極は、例えば金属箔等の負極集電体と、負極集電体上に形成された負極活物質層とを備える。負極集電体には、アルミニウムや銅などの負極の電位範囲で安定な金属の箔、当該金属を表層に配置したフィルム等を用いることができる。負極活物質層は、リチウムイオンを吸蔵・放出可能な負極活物質の他に、結着剤を含むことが好適である。また、必要により導電材を含んでいてもよい。 [Negative electrode]
The negative electrode includes, for example, a negative electrode current collector such as a metal foil, and a negative electrode active material layer formed on the negative electrode current collector. As the negative electrode current collector, a foil of a metal stable in the potential range of the negative electrode such as aluminum or copper, a film in which the metal is disposed on the surface, or the like can be used. The negative electrode active material layer preferably contains a binder in addition to the negative electrode active material capable of inserting and extracting lithium ions. Moreover, you may contain the electrically conductive material as needed.

負極活物質としては、天然黒鉛、人造黒鉛、リチウム、珪素、炭素、錫、ゲルマニウム、アルミニウム、鉛、インジウム、ガリウム、リチウム合金、予めリチウムを吸蔵させた炭素並びに珪素、及びこれらの合金並びに混合物等を用いることができる。結着剤としては、正極の場合と同様にＰＴＦＥ等を用いることもできるが、スチレン−ブタジエン共重合体（ＳＢＲ）又はこの変性体等を用いることが好ましい。結着剤は、ＣＭＣ等の増粘剤と併用されてもよい。   As the negative electrode active material, natural graphite, artificial graphite, lithium, silicon, carbon, tin, germanium, aluminum, lead, indium, gallium, lithium alloy, carbon in which lithium is occluded beforehand, silicon, and alloys and mixtures thereof, etc. Can be used. As the binder, PTFE or the like can be used as in the case of the positive electrode, but it is preferable to use a styrene-butadiene copolymer (SBR) or a modified product thereof. The binding agent may be used in combination with a thickening agent such as CMC.

〔非水電解質〕
非水電解質は、非水溶媒と、非水溶媒に溶解した電解質塩とを含む。非水電解質は、液体電解質（非水電解液）に限定されず、ゲル状ポリマー等を用いた固体電解質であってもよい。非水溶媒には、例えばエステル類、エーテル類、アセトニトリル等のニトリル類、ジメチルホルムアミド等のアミド類、及びこれらの２種以上の混合溶媒等を用いることができる。 [Non-aqueous electrolyte]
The non-aqueous electrolyte comprises a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent. The non-aqueous electrolyte is not limited to a liquid electrolyte (non-aqueous electrolyte), and may be a solid electrolyte using a gel-like polymer or the like. As the non-aqueous solvent, for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, mixed solvents of two or more of them, and the like can be used.

上記エステル類の例としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状炭酸エステル、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネート、エチルプロピルカーボネート、メチルイソプロピルカーボネート等の鎖状炭酸エステル、酢酸メチル、酢酸エチル、酢酸プロピル、プロピオン酸メチル、プロピオン酸エチル、γ−ブチロラクトン等のカルボン酸エステル類などが挙げられる。   Examples of the esters include cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate, linear carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate and methyl isopropyl carbonate, Carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and the like can be mentioned.

上記エーテル類の例としては、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、テトラヒドロフラン、２−メチルテトラヒドロフラン、プロピレンオキシド、１，２−ブチレンオキシド、１，３−ジオキサン、１，４−ジオキサン、１，３，５−トリオキサン、フラン、２−メチルフラン、１，８−シネオール、クラウンエーテル等の環状エーテル、１，２−ジメトキシエタン、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジヘキシルエーテル、エチルビニルエーテル、ブチルビニルエーテル、メチルフェニルエーテル、エチルフェニルエーテル、ブチルフェニルエーテル、ペンチルフェニルエーテル、メトキシトルエン、ベンジルエチルエーテル、ジフェニルエーテル、ジベンジルエーテル、o−ジメトキシベンゼン、１，２−ジエトキシエタン、１，２−ジブトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、１，１−ジメトキシメタン、１，１−ジエトキシエタン、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチル等の鎖状エーテル類などが挙げられる。   Examples of the above ethers include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 -Dioxane, 1,3,5-trioxane, furan, 2-methyl furan, 1, 8-cineole, cyclic ether such as crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl Ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, tri Examples thereof include linear ethers such as ethylene glycol dimethyl ether and tetraethylene glycol dimethyl.

非水溶媒は、上記各種溶媒の水素をフッ素等のハロゲン原子で置換したハロゲン置換体を含有することが好適である。特に、フッ素化環状炭酸エステル、フッ素化鎖状炭酸エステルが好ましく、両者を混合して用いることがより好ましい。これにより、負極はもとより正極においても良好な保護被膜が形成されてサイクル特性が向上する。フッ素化環状炭酸エステルの好適な例としては、４−フルオロエチレンカーボネート、４，５−ジフルオロエチレンカーボネート、４，４−ジフルオロエチレンカーボネート、４，４，５−トリフルオロエチレンカーボネート、４，４，５，５−テトラフルオロエチレンカーボネート等が挙げられる。フッ素化鎖状エステルの好適な例としては、２，２，２−トリフルオロ酢酸エチル、３，３，３−トリフルオロプロピオン酸メチル、ペンタフルオロプロピオン酸メチル等が挙げられる。   The non-aqueous solvent preferably contains a halogen-substituted product in which hydrogen of each of the above-mentioned various solvents is substituted with a halogen atom such as fluorine. In particular, fluorinated cyclic carbonates and fluorinated chain carbonates are preferred, and a mixture of both is more preferred. As a result, a good protective film is formed not only on the negative electrode but also on the positive electrode, and the cycle characteristics are improved. Preferred examples of the fluorinated cyclic carbonate include 4-fluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5. A 5, 5- tetrafluoro ethylene carbonate etc. are mentioned. As preferable examples of the fluorinated chain ester, ethyl 2,2,2-trifluoroacetate, methyl 3,3,3-trifluoropropionate, methyl pentafluoropropionate and the like can be mentioned.

上記電解質塩は、リチウム塩であることが好ましい。リチウム塩の例としては、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＦＳＯ2）2、ＬｉＮ（Ｃ1Ｆ2l+1ＳＯ2）（ＣmＦ2m+1ＳＯ2）（ｌ，ｍは１以上の整数）、ＬｉＣ（ＣPＦ2p+1ＳＯ2）（ＣqＦ2q+1ＳＯ2）（ＣrＦ2r+1ＳＯ2）（p，q，rは１以上の整数）、Ｌｉ[Ｂ(Ｃ2Ｏ4)2]（ビス（オキサレート）ホウ酸リチウム(ＬｉＢＯＢ)）、Ｌｉ[Ｂ(Ｃ2Ｏ4)Ｆ2] 、Ｌｉ[Ｐ(Ｃ2Ｏ4)Ｆ4]、Ｌｉ[Ｐ(Ｃ2Ｏ4)2Ｆ2]等が挙げられる。これらのリチウム塩は、１種類で使用してもよく、２種類以上を組み合わせて使用してもよい。 The electrolyte salt is preferably a lithium salt. Examples of lithium salts include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 2) (l, m is an integer of 1 or more), LiC (C P F 2p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2) (p, q, r Is an integer of 1 or more), Li [B (C 2 O 4 ) 2 ] (lithium bis (oxalate) borate (LiBOB)), Li [B (C 2 O 4 ) F 2 ], Li [P (C 2) O 4 ) F 4 ], Li [P (C 2 O 4 ) 2 F 2 ], etc. may be mentioned. These lithium salts may be used alone or in combination of two or more.

〔セパレータ〕
セパレータには、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータの材質としては、ポリエチレン、ポリプロピレン等のオレフィン系樹脂、セルロースなどが好適である。セパレータは、セルロース繊維層及びオレフィン系樹脂等の熱可塑性樹脂繊維層を有する積層体であってもよい。 [Separator]
For the separator, a porous sheet having ion permeability and insulation is used. Specific examples of the porous sheet include a microporous thin film, a woven fabric, a non-woven fabric and the like. As a material of the separator, olefin resins such as polyethylene and polypropylene, cellulose and the like are preferable. The separator may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.

以下、実施例により本開示をさらに詳説するが、本開示はこれらの実施例に限定されるものではない。   Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

＜実施例１＞
［Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体（正極活物質）の作製］
ＮｉＳＯ4、ＣｏＳＯ4、及びＭｎＳＯ4を１３．５：１３．５：７３の化学量論比となるように水溶液中で混合し、共沈させることで前駆体物質である（Ｎｉ，Ｃｏ，Ｍｎ）（ＯＨ）2を得た。次に、この前駆体物質、Ｎａ2ＣＯ3、及びＬｉＯＨ・Ｈ2Ｏを８５：７４：１５の化学量論比となるように混合し、さらに追加のＬｉＯＨ・Ｈ2Ｏを混合した後、この混合物を９００℃で１０時間保持して、ナトリウム複合酸化物を合成した。ＬｉＯＨ・Ｈ2Ｏの追加分は、ナトリウム複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が０．００３５となるように添加量を調整した。 Example 1
[Preparation of Li 2 MnO 3 -LiMO 2 Solid Solution (Positive Electrode Active Material)]
A precursor substance is obtained by mixing NiSO 4 , CoSO 4 , and MnSO 4 in an aqueous solution so as to have a stoichiometric ratio of 13.5: 13.5: 73 and coprecipitating (Ni, Co, Mn ) (OH) 2 was obtained. Next, after mixing this precursor substance, Na 2 CO 3 , and LiOH · H 2 O to a stoichiometric ratio of 85:74:15 and further mixing additional LiOH · H 2 O, This mixture was kept at 900 ° C. for 10 hours to synthesize sodium complex oxide. The addition amount of LiOH · H 2 O was adjusted so that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the sodium composite oxide was 0.0035.

誘導結合プラズマ（ＩＣＰ）発光分光分析装置（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製、商品名「ｉＣＡＰ６３００」）を用いて、得られたナトリウム複合酸化物の組成を分析した。その結果、Ｎａ：Ｌｉ：Ｍｎ：Ｃｏ：Ｎｉ＝０．７５６：０．１４５：０．６２５：０．１１５：０．１１５であった。   The composition of the obtained sodium composite oxide was analyzed using an inductively coupled plasma (ICP) emission spectrophotometer (manufactured by Thermo Fisher Scientific, trade name “iCAP6300”). As a result, it was Na: Li: Mn: Co: Ni = 0.756: 0.145: 0.625: 0.115: 0.115.

粉末Ｘ線回折装置（リガク社製、商品名「ＲＩＮＴ２２００」）を用いて、得られたナトリウム複合酸化物のピーク強度比Ｒ(b/a)を求めた。その結果、当該ナトリウム複合酸化物のＸ線回折パターンには、２θ＝１６°〜１７°にピークトップを有する第１ピーク、及び２θ＝１８°〜１９°にピークトップを有する第２ピークが確認され、ピーク強度比Ｒ(b/a)は０．００３６であった。 The peak intensity ratio R (b / a) of the obtained sodium composite oxide was determined using a powder X-ray diffractometer (manufactured by RIGAKU Co., Ltd., trade name “RINT 2200”). As a result, in the X-ray diffraction pattern of the sodium composite oxide, it is confirmed that the first peak having a peak top at 2θ = 16 ° to 17 ° and the second peak having a peak top at 2θ = 18 ° to 19 ° The peak intensity ratio R (b / a) was 0.0036.

次に、硝酸リチウムと塩化リチウムを８８：１２のモル比で混合した溶融塩床を、合成したナトリウム複合酸化物５ｇに対し５倍当量（２５ｇ）加えた。その後、当該混合物を２８０℃で２時間保持させ、ナトリウム複合酸化物のＮａをＬｉにイオン交換して、リチウム過剰型のリチウム複合酸化物（Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体）を作製した。 Next, a molten salt bed in which lithium nitrate and lithium chloride were mixed at a molar ratio of 88:12 was added 5-fold equivalent (25 g) to 5 g of the synthesized sodium composite oxide. Then, the mixture was kept at 280 ° C. for 2 hours to ion-exchange Na of sodium complex oxide to Li to prepare a lithium excess type lithium complex oxide (Li 2 MnO 3 -LiMO 2 solid solution).

上記ＩＣＰ発光分光分析装置を用いて、得られたリチウム複合酸化物組成を分析した。その結果、Ｎａ：Ｌｉ：Ｍｎ：Ｃｏ：Ｎｉ＝０．０００５：０．８８９：０．６２５：０．１１５：０．１１５であった。   The obtained lithium composite oxide composition was analyzed using the above-mentioned ICP emission spectrophotometer. As a result, it was Na: Li: Mn: Co: Ni = 0.0005: 0.889: 0.625: 0.115: 0.115.

上記粉末Ｘ線回折装置を用いて、得られたリチウム複合酸化物のピーク強度比Ｒ(B/A)を求めた。その結果、当該リチウム複合酸化物のＸ線回折パターンには、２θ＝１８°〜１９°にそれぞれピークトップを含む２つのピークが確認され、ピーク強度比Ｒ(B/A)は０．００７であった。結晶構造解析の結果、主たる結晶構造は、空間群Ｐ６3ｍｃに属するＯ２構造であり、０．４％のｃｃｐ構造（ピーク強度比Ｒ(B/A)に基づいて算出）を含むことが分かった。また、リートベルト解析から、当該リチウム複合酸化物は、Ｌｉ0.744Ｎａ0.0005[Ｌｉ0.145Ｍｎ0.625Ｃｏ0.115Ｎｉ0.115]Ｏ2で表されるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であることが確認された。 The peak intensity ratio R (B / A) of the obtained lithium composite oxide was determined using the above-mentioned powder X-ray diffractometer. As a result, in the X-ray diffraction pattern of the lithium composite oxide, two peaks each including a peak top are confirmed at 2θ = 18 ° to 19 °, and the peak intensity ratio R (B / A) is 0.007. there were. As a result of crystal structure analysis, it is found that the main crystal structure is an O2 structure belonging to the space group P6 3 mc and includes a 0.4% ccp structure (calculated based on peak intensity ratio R (B / A)) The Moreover, the Rietveld analysis, the lithium composite oxide, it was confirmed that the Li 2 MnO 3 -LiMO 2 solid solution represented by Li 0.744 Na 0.0005 [Li 0.145 Mn 0.625 Co 0.115 Ni 0.115] O 2.

［電解液の調整］
４−フルオロエチレンカーボネート（ＦＥＣ）と、フルオロエチルメチルカーボネート（ＦＥＭＣ）とを体積比が１：３となるように混合して非水溶媒を得た。当該非水溶媒に、電解質塩としてＬｉＰＦ6を１．０ｍｏｌ／Ｌの濃度になるように溶解させて電解液を作製した。 [Adjustment of electrolyte]
A non-aqueous solvent was obtained by mixing 4-fluoroethylene carbonate (FEC) and fluoroethyl methyl carbonate (FEMC) in a volume ratio of 1: 3. An electrolyte was prepared by dissolving LiPF 6 as an electrolyte salt to a concentration of 1.0 mol / L in the non-aqueous solvent.

［コイン型非水電解質二次電池の作製］
以下の手順により、図３に示すコイン型非水電解質二次電池１０（以下、「コイン型電池１０」という）を作製した。まず、得られたＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体を正極活物質、アセチレンブラックを導電剤、ポリフッ化ビニリデンを結着剤として、正極活物質、導電剤、結着剤の質量比が８０：１０：１０となるように混合した。次に、当該混合物をＮ−メチル−２−ピロリドンを用いてスラリー化した。このスラリーを正極集電体であるアルミニウム箔集電体上に塗布し、１１０℃で真空乾燥して正極１１を作製した。 [Fabrication of coin-type non-aqueous electrolyte secondary battery]
According to the following procedure, coin-type non-aqueous electrolyte secondary battery 10 (hereinafter referred to as "coin-type battery 10") shown in FIG. 3 was produced. First, using the obtained Li 2 MnO 3 -LiMO 2 solid solution as a positive electrode active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder, the mass ratio of the positive electrode active material, the conductive agent, and the binder is 80:10. It mixed so that it might become: 10. The mixture was then slurried with N-methyl-2-pyrrolidone. The slurry was applied onto an aluminum foil current collector, which was a positive electrode current collector, and vacuum dried at 110 ° C. to produce a positive electrode 11.

次に、封口板１２及びケース１３を有する電池外装体を用意し、露点−５０℃以下のドライエアー下で、封口板１２の内面に厚さ０．３ｍｍのリチウム金属箔を負極１４として貼り付けた。負極１４上にセパレータ１５を配置し、続いて正極活物質層がセパレータ１５と対向するように正極１１を配置した。さらに正極１１のセパレータ１５と反対側に、ステンレス製の当て板１６及び皿バネ１７を配置した。そして、調整した電解液を封口板１２の凹部に満たした後、封口板１２にガスケット１８及びケース１３を取り付けて、コイン型電池１０を作製した。   Next, a battery outer body having the sealing plate 12 and the case 13 is prepared, and a 0.3 mm thick lithium metal foil is attached as the negative electrode 14 to the inner surface of the sealing plate 12 under dry air with a dew point of -50.degree. The The separator 15 was disposed on the negative electrode 14, and then the positive electrode 11 was disposed such that the positive electrode active material layer faced the separator 15. Further, on the opposite side of the positive electrode 11 to the separator 15, a stainless steel backing plate 16 and a disc spring 17 were disposed. Then, after the adjusted electrolytic solution was filled in the concave portion of the sealing plate 12, the gasket 18 and the case 13 were attached to the sealing plate 12, and the coin-type battery 10 was manufactured.

ナトリウム複合酸化物のピーク強度比Ｒ(b/a)、Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体のピーク強度比Ｒ(B/A)、及びＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体に含まれるｃｃｐ構造の含有量は、後述の放電容量と共に表１に示した（以下の実施例、比較例についても同様）。 Peak intensity ratio R of the sodium complex oxide (b / a), containing Li 2 MnO 3 -LiMO 2 solid solution of the peak intensity ratio R (B / A), and Li 2 ccp structure contained in MnO 3 -LiMO 2 solid solution The amounts are shown in Table 1 together with the discharge capacity described later (the same applies to the following examples and comparative examples).

＜実施例２〜５＞
ナトリウム複合酸化物の合成において、当該複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が目標値となるように、ＬｉＯＨ・Ｈ2Ｏの追加分の添加量をそれぞれ調整した以外は、実施例１と同様にして、コイン型電池を作製した。なお、表１に示すピーク強度比Ｒ(b/a)は、粉末Ｘ線回折測定により得られた分析結果であり、目標値は当該値に近似する値である（以下同様）。 Examples 2 to 5
In the synthesis of the sodium complex oxide, the addition amount of the additional portion of LiOH · H 2 O was adjusted so that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the complex oxide becomes a target value. A coin-type battery was produced in the same manner as Example 1 except for the above. The peak intensity ratio R (b / a) shown in Table 1 is an analysis result obtained by powder X-ray diffraction measurement, and the target value is a value approximating the value (the same applies hereinafter).

上記粉末Ｘ線回折装置を用いて、実施例２〜５で得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、ピーク強度比Ｒ(B/A)はそれぞれ表１に示す値であった。
なお、得られたリチウム複合酸化物は、実施例１の場合と同じ組成を有するＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であった。 As a result of measuring the X-ray diffraction pattern of the lithium composite oxide obtained in Examples 2 to 5 using the above powder X-ray diffractometer, the peak intensity ratio R (B / A) is as shown in Table 1 there were.
The obtained lithium composite oxide was a Li 2 MnO 3 -LiMO 2 solid solution having the same composition as in Example 1.

＜実施例６〜１１＞
ＮｉＳＯ4、ＣｏＳＯ4、及びＭｎＳＯ4を６．５：１３．５：８０の化学量論比となるように水溶液中で混合し、共沈させることで前駆体物質である（Ｎｉ，Ｃｏ，Ｍｎ）（ＯＨ）2を得た。次に、この前駆体物質、Ｎａ2ＣＯ3、及びＬｉＯＨ・Ｈ2Ｏを８５：７４：１５の化学量論比となるように混合し、さらに追加のＬｉＯＨ・Ｈ2Ｏを混合した後、この混合物を９００℃で１０時間保持して、ナトリウム複合酸化物を合成した。このとき、ナトリウム複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が目標値（表１に示す値）となるように、ＬｉＯＨ・Ｈ2Ｏの追加分の添加量をそれぞれ調整した。
以上の工程以外は、実施例１と同様にして、コイン型電池を作製した。 Examples 6 to 11
It is a precursor substance by mixing NiSO 4 , CoSO 4 , and MnSO 4 in an aqueous solution to have a stoichiometry ratio of 6.5: 13.5: 80 and coprecipitating (Ni, Co, Mn ) (OH) 2 was obtained. Next, after mixing this precursor substance, Na 2 CO 3 , and LiOH · H 2 O to a stoichiometric ratio of 85:74:15 and further mixing additional LiOH · H 2 O, This mixture was kept at 900 ° C. for 10 hours to synthesize sodium complex oxide. At this time, the addition amount of LiOH · H 2 O is added so that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the sodium composite oxide becomes a target value (the value shown in Table 1). It was adjusted.
A coin-type battery was produced in the same manner as in Example 1 except for the above steps.

上記ＩＣＰ発光分光分析装置を用いて、実施例６〜１１で得られたリチウム複合酸化物の組成を分析した結果、いずれもＮａ：Ｌｉ：Ｍｎ：Ｃｏ：Ｎｉ＝０．０００４：０．９３２：０．６６６：０．１１２：０．０５４であった。
上記粉末Ｘ線回折装置を用いて、実施例６〜１１で得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、ピーク強度比Ｒ(B/A)はそれぞれ表１に示す値であった。
また、リートベルト解析から、当該リチウム複合酸化物は、いずれもＬｉ0.765Ｎａ0.0004[Ｌｉ0.167Ｍｎ0.666Ｃｏ0.112Ｎｉ0.054]Ｏ2で表されるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であることが確認された。 As a result of analyzing the composition of the lithium composite oxide obtained in Examples 6 to 11 using the above-mentioned ICP emission spectrochemical analysis device, it is found that each of Na: Li: Mn: Co: Ni = 0.0004: 0.932: It was 0.666: 0.112: 0.054.
As a result of measuring the X-ray diffraction pattern of the lithium composite oxide obtained in Examples 6 to 11 using the above powder X-ray diffractometer, the peak intensity ratio R (B / A) is as shown in Table 1 respectively. there were.
Further, from the Rietveld analysis, it is confirmed that the lithium composite oxide is a Li 2 MnO 3 -LiMO 2 solid solution represented by Li 0.765 Na 0.0004 [Li 0.167 Mn 0.666 Co 0.112 Ni 0.054 ] O 2. The

＜実施例１２〜１６＞
ＮｉＳＯ4、ＣｏＳＯ4、及びＭｎＳＯ4を１３．５：６．５：８０の化学量論比となるように水溶液中で混合し、共沈させることで前駆体物質である（Ｎｉ，Ｃｏ，Ｍｎ）（ＯＨ）2を得た。次に、この前駆体物質、Ｎａ2ＣＯ3、及びＬｉＯＨ・Ｈ2Ｏを８５：７４：１５の化学量論比となるように混合し、さらに追加のＬｉＯＨ・Ｈ2Ｏを混合した後、この混合物を９００℃で１０時間保持して、ナトリウム複合酸化物を合成した。このとき、ナトリウム複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が、目標値（表１に示す値）となるように、ＬｉＯＨ・Ｈ2Ｏの追加分の添加量をそれぞれ調整した。
以上の工程以外は、実施例１と同様にして、コイン型電池を作製した。 Examples 12 to 16
A precursor substance is obtained by mixing NiSO 4 , CoSO 4 , and MnSO 4 in an aqueous solution so as to have a stoichiometric ratio of 13.5: 6.5: 80 (Ni, Co, Mn ) (OH) 2 was obtained. Next, after mixing this precursor substance, Na 2 CO 3 , and LiOH · H 2 O to a stoichiometric ratio of 85:74:15 and further mixing additional LiOH · H 2 O, This mixture was kept at 900 ° C. for 10 hours to synthesize sodium complex oxide. At this time, the addition amount of LiOH · H 2 O was added so that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the sodium composite oxide becomes the target value (the value shown in Table 1). I adjusted each.
A coin-type battery was produced in the same manner as in Example 1 except for the above steps.

上記ＩＣＰ発光分光分析装置を用いて、実施例１２〜１６で得られたリチウム複合酸化物の組成を分析した結果、いずれもＮａ：Ｌｉ：Ｍｎ：Ｃｏ：Ｎｉ＝０．０００４：０．８９６：０．６８４：０．０５６：０．１１５であった。
上記粉末Ｘ線回折装置を用いて、実施例１２〜１６で得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、ピーク強度比Ｒ(B/A)はそれぞれ表１に示す値であった。また、リートベルト解析から、当該リチウム複合酸化物は、いずれもＬｉ0.751Ｎａ0.0004[Ｌｉ0.145Ｍｎ0.684Ｃｏ0.056Ｎｉ0.115]Ｏ2で表されるＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であることが確認された。 As a result of analyzing the composition of the lithium composite oxide obtained in Examples 12 to 16 using the above-mentioned ICP emission spectrochemical analysis device, it is found that each of Na: Li: Mn: Co: Ni = 0.0004: 0.896: It was 0.684: 0.056: 0.115.
As a result of measuring the X-ray diffraction pattern of the lithium composite oxide obtained in Examples 12 to 16 using the above powder X-ray diffractometer, the peak intensity ratio R (B / A) is as shown in Table 1 respectively. there were. Further, it is confirmed from the Rietveld analysis that the lithium composite oxide is a Li 2 MnO 3 -LiMO 2 solid solution represented by Li 0.751 Na 0.0004 [Li 0.145 Mn 0.684 Co 0.056 Ni 0.115 ] O 2. The

＜比較例１＞
ナトリウム複合酸化物の合成において、追加のＬｉＯＨ・Ｈ2Ｏを添加しなかった以外は、実施例１と同様にして、コイン型電池を作製した。 Comparative Example 1
A coin battery was fabricated in the same manner as Example 1, except that in the synthesis of the sodium composite oxide, no additional LiOH.H 2 O was added.

上記粉末Ｘ線回折装置を用いて、得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、高角度側ピークは確認できなかった（ピーク強度比Ｒ(B/A)は０）。
なお、得られたリチウム複合酸化物は、実施例１の場合と同じ組成を有するＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であった。 As a result of measuring the X-ray diffraction pattern of the obtained lithium composite oxide using the above-mentioned powder X-ray diffractometer, a high angle side peak could not be confirmed (peak intensity ratio R (B / A) is 0).
The obtained lithium composite oxide was a Li 2 MnO 3 -LiMO 2 solid solution having the same composition as in Example 1.

＜比較例２＞
ナトリウム複合酸化物の合成において、追加のＬｉＯＨ・Ｈ2Ｏを添加しなかった以外は、実施例１２と同様にして、コイン型電池を作製した。 Comparative Example 2
A coin battery was fabricated in the same manner as Example 12, except that in the synthesis of the sodium composite oxide, no additional LiOH.H 2 O was added.

上記粉末Ｘ線回折装置を用いて、得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、高角度側ピークは確認できなかった（ピーク強度比Ｒ(B/A)は０）。
なお、得られたリチウム複合酸化物は、実施例１２の場合と同じ組成を有するＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であった。 As a result of measuring the X-ray diffraction pattern of the obtained lithium composite oxide using the above-mentioned powder X-ray diffractometer, a high angle side peak could not be confirmed (peak intensity ratio R (B / A) is 0).
The obtained lithium composite oxide was a Li 2 MnO 3 -LiMO 2 solid solution having the same composition as in Example 12.

＜比較例３，４＞
ナトリウム複合酸化物の合成において、当該複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が目標値（表１に示す値）となるように、ＬｉＯＨ・Ｈ2Ｏの追加分の添加量をそれぞれ調整した以外は、実施例１と同様にして、コイン型電池を作製した。 <Comparative Examples 3 and 4>
In the synthesis of the sodium complex oxide, the additional component of LiOH · H 2 O such that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the complex oxide becomes a target value (the value shown in Table 1) A coin-type battery was produced in the same manner as in Example 1 except that the addition amount of each was adjusted.

上記粉末Ｘ線回折装置を用いて、比較例３，４で得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、ピーク強度比Ｒ(B/A)はそれぞれ表１に示す値であった。
なお、得られたリチウム複合酸化物は、実施例１の場合と同じ組成を有するＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であった。 As a result of measuring the X-ray diffraction pattern of the lithium composite oxide obtained in Comparative Examples 3 and 4 using the above powder X-ray diffractometer, the peak intensity ratio R (B / A) is as shown in Table 1 respectively. there were.
The obtained lithium composite oxide was a Li 2 MnO 3 -LiMO 2 solid solution having the same composition as in Example 1.

＜比較例５＞
ナトリウム複合酸化物の合成において、当該複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)が目標値（表１に示す値）となるように、ＬｉＯＨ・Ｈ2Ｏの追加分の添加量を調整した以外は、実施例６と同様にして、コイン型電池を作製した。 Comparative Example 5
In the synthesis of the sodium complex oxide, the additional component of LiOH · H 2 O such that the peak intensity ratio R (b / a) in the X-ray diffraction pattern of the complex oxide becomes a target value (the value shown in Table 1) A coin-type battery was produced in the same manner as in Example 6, except that the addition amount of was adjusted.

上記粉末Ｘ線回折装置を用いて、得られたリチウム複合酸化物のＸ線回折パターンを測定した結果、ピーク強度比Ｒ(B/A)はそれぞれ表１に示す値であった。
なお、得られたリチウム複合酸化物は、実施例６の場合と同じ組成を有するＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体であった。 As a result of measuring the X-ray-diffraction pattern of the obtained lithium complex oxide using the said powder X-ray-diffraction apparatus, peak intensity ratio R (B / A) was a value shown in Table 1, respectively.
Incidentally, the lithium composite oxide obtained was Li 2 MnO 3 -LiMO 2 solid solution having the same composition as in Example 6.

［放電容量の評価］
実施例及び比較例で作製したコイン型電池について、１５ｍＡ／ｇの定電流で電池電圧が４．７Ｖに達するまで充電した後、１５ｍＡ／ｇの定電流で電池電圧が２．０Ｖに達するまで放電を行い、このときの放電容量を求めた。充放電試験は、ソーラトロン社製の電気化学測定システムを用いて行った。評価結果は表１に示した。 [Evaluation of discharge capacity]
About the coin type battery produced by the example and the comparative example, after charging until the battery voltage reaches 4.7V with a constant current of 15 mA / g, discharging until the battery voltage reaches 2.0 V with a constant current of 15 mA / g And the discharge capacity at this time was determined. The charge and discharge test was performed using an electrochemical measurement system manufactured by Solartron. The evaluation results are shown in Table 1.

Figure 0006531936
※正極活物質に含有される遷移金属の組成
Ｍ１ Ｍｎ：Ｎｉ：Ｃｏ＝７３：１３．５：１３．５
Ｍ２ Ｍｎ：Ｎｉ：Ｃｏ＝８０：６．５：１３．５
Ｍ３ Ｍｎ：Ｎｉ：Ｃｏ＝８０：１３．５：６．５
Figure 0006531936
 ※ Composition of transition metal contained in positive electrode active material M1 Mn: Ni: Co = 73: 13.5: 13.5
M2 Mn: Ni: Co = 80: 6.5: 13.5
M3 Mn: Ni: Co = 80: 13.5: 6.5

表１に示すデータに基づいて、図４及び図５を作製した。
図４は、実施例及び比較例で作製したコイン型電池において、正極活物質のＸ線回折パターンにおけるピーク強度比Ｒ(B/A)×１００と、放電容量との関係を示す図である。図５は、正極活物質の作製に用いられるナトリウム複合酸化物のＸ線回折パターンにおけるピーク強度比Ｒ(b/a)×１００と、放電容量との関係を示す図である。 4 and 5 were produced based on the data shown in Table 1.
FIG. 4 is a view showing the relationship between the discharge capacity and the peak intensity ratio R (B / A) × 100 in the X-ray diffraction pattern of the positive electrode active material in the coin-type battery fabricated in the example and the comparative example. FIG. 5 is a view showing the relationship between the discharge capacity and the peak intensity ratio R (b / a) × 100 in the X-ray diffraction pattern of the sodium composite oxide used for producing the positive electrode active material.

図４から明らかであるように、ピーク強度比Ｒ(B/A)が０．００１＜Ｒ(B/A)＜０．０３（０．１＜Ｒ(B/A)×１００＜３）を満たす実施例のコイン型電池は、当該条件を満たさない比較例のコイン型電池に対して、放電容量が特異的に向上している。即ち、ピーク強度比Ｒ(B/A)が０．００１未満である場合（比較例１，２）、ピーク強度比Ｒ(B/A)が０．０３を超える場合（比較例３〜４）のいずれにおいても、当該条件を満たす場合に比べて放電容量が低下する。特に、ピーク強度比Ｒ(B/A)が０．０３を超える場合は放電容量の低下が大きくなる。 As apparent from FIG. 4, the peak intensity ratio R (B / A) satisfies 0.001 <R (B / A) <0.03 (0.1 <R (B / A) × 100 <3). The coin-type battery of the Example which satisfy | fills the discharge capacity is improving specifically with respect to the coin-type battery of the comparative example which does not satisfy | fill the said conditions. That is, when peak intensity ratio R (B / A) is less than 0.001 (comparative examples 1 and 2), peak intensity ratio R (B / A) exceeds 0.03 (comparative examples 3 and 4) In any of the above, the discharge capacity is reduced compared to the case where the condition is satisfied. In particular, when the peak intensity ratio R (B / A) exceeds 0.03, the decrease in discharge capacity becomes large.

上記のように、低角度側ピーク（強度Ａ）は、例えばＯ２構造に起因し、高角度側ピーク（強度Ｂ）は、例えばＯ３構造等のｃｃｐ構造に起因するものであるから、正極活物質は主たる結晶構造がＯ２構造であり、ｃｃｐ構造をわずかに含む場合に、放電容量が特異的に向上する。この特異的な効果は、主たる結晶構造をＯ２構造とすることで遷移金属のマイグレーションが抑制され、ｃｃｐ構造をわずかに含有させることで遷移金属層におけるＬｉの移動が促進されたことによると考えられる。つまり、正極活物質の結晶構造を純粋なＯ２構造とするのではなく、わずかなｃｃｐ構造を意図的に作ることで、高い放電容量を得ることができる。一方、ｃｃｐ構造の含有量が１．９体積％よりも多いと放電容量がかえって低下する。このように、放電容量の特異的な向上は、ｃｃｐ構造の含有量が０．０３〜１．９体積％（又は０．０５〜１．８体積％）という極めて限定された範囲内でのみ得られる。   As described above, the low angle side peak (intensity A) originates from, for example, the O 2 structure, and the high angle side peak (intensity B) originates from, for example, the ccp structure such as the O 3 structure. The discharge capacity is specifically improved when the main crystal structure is the O2 structure and the cpp structure is slightly contained. This specific effect is considered to be due to the fact that the transition metal migration is suppressed by making the main crystal structure an O 2 structure, and the migration of Li in the transition metal layer is promoted by a slight inclusion of the ccp structure. . That is, a high discharge capacity can be obtained by intentionally forming a slight ccp structure instead of making the crystal structure of the positive electrode active material a pure O 2 structure. On the other hand, when the content of the ccp structure is more than 1.9% by volume, the discharge capacity is rather reduced. Thus, the specific improvement of the discharge capacity can be obtained only within a very limited range of the content of the ccp structure of 0.03 to 1.9% by volume (or 0.05 to 1.8% by volume). Be

なお、図５に示すように、ピーク強度比Ｒ(b/a)が０．００１＜Ｒ(b/a)＜０．０２８（０．１＜Ｒ(B/A)×１００＜２．８）を満たすナトリウム複合酸化物を用いた場合に、当該条件を満たさないナトリウム複合酸化物を用いた比較例のコイン型電池に対して、放電容量が特異的に向上している。 As shown in FIG. 5, the peak intensity ratio R (b / a) is 0.001 <R (b / a) <0.028 (0.1 <R (B / A) × 100 <2.8 ). The discharge capacity is specifically improved with respect to the coin-type battery of the comparative example using the sodium complex oxide which does not satisfy | fill the said conditions, when the sodium complex oxide which satisfy | fills (1) satisfy | fills.

１０ コイン型非水電解質二次電池、１１ 正極、１２ 封口板、１３ ケース、１４負極、１５ セパレータ、１６ 当て板、１７ 皿バネ、１８ ガスケット

DESCRIPTION OF SYMBOLS 10 coin-type non-aqueous electrolyte secondary battery, 11 positive electrodes, 12 sealing plates, 13 cases, 14 negative electrodes, 15 separators, 16 backing plates, 17 disc springs, 18 gaskets

Claims (4)

Ｘ線回折パターンの回折角１８°〜１９°にそれぞれピークトップがある２つのピークを持ち、当該各ピークのうち、低角度側ピークの強度Ａに対する高角度側ピークの強度Ｂの比Ｒ(B/A)が０．００１＜Ｒ(B/A)＜０．０３を満たすＬｉ2ＭｎＯ3−ＬｉＭＯ2固溶体｛Ｍは少なくとも１種の金属元素｝を含み、
前記Ｌｉ 2 ＭｎＯ 3 −ＬｉＭＯ 2 固溶体は、一般式Ｌｉ x Ｎａ y [Ｌｉ z1 Ｍｎ z2 Ｍ * (1-z1-z2) ]Ｏ (2 ±γ ) ｛０．６７＜ｘ＜１．１、０＜ｙ＜０．１、０＜ｚ１＜０．３３、０．５＜ｚ２＜０．９５、０≦γ＜０．１、Ｍ * は少なくともＮｉ、Ｃｏを含む、２種以上の金属元素｝で表される、非水電解質二次電池用正極活物質。 Has two peaks, each with peak top at a diffraction angle 18 ° ~ 19 ° in X-ray diffraction pattern, of the respective peak, the ratio of the intensity B of the high angle side peak to the intensity A of the low angle side peak R (B / a) viewed contains a is 0.001 <R (B / a) satisfy <0.03 Li 2 MnO 3 -LiMO 2 solid solution {M is at least one metal element},
The Li 2 MnO 3 -LiMO 2 solid solution is represented by the general formula Li x Na y [Li z1 Mn z2 M * (1-z1-z2)] O (2 ± γ) {0.67 <x <1.1,0 <Y <0.1, 0 <z1 <0.33, 0.5 <z2 <0.95, 0 ≦ γ <0.1, M * contains at least Ni and Co, and two or more metal elements} The positive electrode active material for nonaqueous electrolyte secondary batteries represented by these. 前記Ｌｉ2ＭｎＯ3−ＬｉＭＯ2固溶体は、前記非水電解質二次電池用正極活物質の総体積に対して５０体積％以上含まれている請求項１に記載の非水電解質二次電池用正極活物質。 The positive electrode for a non-aqueous electrolyte secondary battery according to claim 1, wherein the Li 2 MnO 3 -LiMO 2 solid solution is contained in an amount of 50% by volume or more based on the total volume of the positive electrode active material for the non-aqueous electrolyte secondary battery. Active material. 請求項１又は２に記載の非水電解質二次電池用正極活物質を含む正極と、負極と、電解質と、を備えた非水電解質二次電池。 Positive electrode and a negative electrode, a nonaqueous electrolyte secondary battery including an electrolyte, a containing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 1 or 2. 一般式Ｎａα[Ｌｉβ1Ｍｎβ2Ｍ(1-β1-β2)]Ｏ(2±γ)｛０．６７＜α＜１．１、０＜β１＜０．３３、０．５＜β２＜０．９５、０≦γ＜０．１、Ｍは少なくとも１種の金属元素｝で表され、Ｘ線回折パターンの回折角１６°〜１７°にピークトップがある第１ピークの強度ａに対する、回折角１８°〜１９°にピークトップがある第２ピークの強度ｂの比Ｒ(b/a)が０．００１＜Ｒ(b/a)＜０．０２８を満たすナトリウム複合酸化物を合成する工程と、
前記ナトリウム複合酸化物とリチウム化合物とを反応させて、前記ナトリウム複合酸化物のＮａをＬｉにイオン交換する工程と、
を含む非水電解質二次電池用正極活物質の製造方法。 Formula Naα [Liβ 1 Mnβ 2 M ( 1- β 1- β 2)] O (2 ± γ) {0.67 <α <1.1,0 <β1 <0.33,0.5 <β2 < 0.95, 0 ≦ γ <0.1, M is at least one metal element}, and the intensity a of the first peak having a peak top at the diffraction angle 16 ° to 17 ° of the X-ray diffraction pattern, Synthesize a sodium composite oxide in which the ratio R (b / a) of the intensity b of the second peak having a peak top at a diffraction angle of 18 ° to 19 ° satisfies 0.001 <R (b / a) <0.028 Process,
Reacting the sodium complex oxide with a lithium compound to ion exchange Na of the sodium complex oxide to Li;
A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, comprising:
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